• Economic and Environmental Geology
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• v.15 no.4
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• pp.205-219
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• 1982

The Eosangcheon manganese ore deposits occur as supergene weathering deposits along quartz porphyry dikes developed in the Ordovician Heungweolri dolomite and Samtaesan limestone formations. The manganese ores are composed of manganese oxide minerals and associated other minerals. Rancieite and todorokite are abundantly found, and birnessite, nsutite, pyrolusite and chalcophanite are found in minor quantities. Associated other minerals are calcite, gypsum, goethite, lepidocrosite, quartz, and sericite. Microscopic, chemical, X-ray powder diffraction, infrared absorption spectroscopic and differential thermal analyses have been made for manganese oxide minerals and associated other minerals. The relationship of birnessite and rancieite was studied by means of X-ray powder diffraction and infrared absorption spectroscopic analyses. It is assumed that these minerals are closely related to each other in crystal structure, but separate species. The manganese oxide minerals were formed mainly by replacement, precipitation from solution, and recrystallization in the supergene weathering environment. The trend of formation of manganese oxide minerals is: (Rhodochrosite)-(todorokite)-(birnessite, rancieite)-(nsutite, pyrolusite, chalcophanite).

• Economic and Environmental Geology
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• v.18 no.4
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• pp.331-342
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• 1985

The Dongbo tungsten-molybdenum deposits are fissure-filling veins emplaced in granites of late Cretaceous age. Integrated field, mineralogic and fluid inclusion studies were undertaken to illuminate the characters and origin of the ore deposits. Mineral paragenesis is complicated by repeated fracturing, but four distinct depositional stages can be recognized; (I) tungsten-molybdenum minerals-quartz-chlorite stage, (II) iron-oxide and sulfides-quartz stage, (III) iron -oxide-base metal sulfides-sulfosalts-quartz-carbonates stage, (IV) barren rhodochrosite-zeolite stage. Fluid inclusion studies were carried out for stage I quartz and stage III quartz, sphalerite and calcite. Fluid inclusion studies reveals highly systematic trends of homogenization temperature and salinity throughout the mineralization. Ore fluids during stage I were complex, NaCl rich brine and salinity reached values as high as 34.4 weight percent equivalent NaCl, but the later ore fluids were more dilute and reached to 9.7 weight percent equivalent NaCl during stage III. Intermittent boiling of ore fluid during stage I is indicated by the fluid inclusions in stage I quartz. Depositional temperatures and pressures during stage I range from $520^{\circ}C$ to $265^{\circ}C$and from 600 to 400 bars. Homogenization temperatures of the stage III quartz, sphalerite and calcite range from $305^{\circ}C$ to $190^{\circ}C$. Fluid inclusion data from the Dongbo mine are nearly similar to those from other hydrothermal tungsten deposits in the Kyeongsang basin. Depositional temperature and salinity of ore fluids during precipitation of tungsten-molybdenum minerals in Dongbo mine were much higher, but $CO_2$ contents were much lower than those from hydrothermal tungsten-molybdenum deposits of late Cretaceous plutonic association in central parts of Korean peninsula.

• Economic and Environmental Geology
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• v.51 no.5
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• pp.401-407
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• 2018

For the treatment of heavy metals in the mine drainage from the closed mine area, various methods such as passive, active and semi-active treatments are considered. Among contaminated elements in the mine drainage, Mn is one of the difficult elements for the treatment because it needs high pH over 9.0 for its concentration to be reduced. In this study, the efficiency of various slag complex reactors (slag (S), slag+limestone (SL) and slag+Mn coated gravel (SG)) on Mn removal in the presence of Fe, which is a competitive element with Mn, was evaluated to investigate effective methods for the treatment of Mn in mine drainage. As a result of experiments on Mn removal without Fe during 358 days, using influent with $30{\sim}50Mn{\cdot}mg/L$ and pH 6.7 on the average, S reactor showed continuously high Mn removal efficiency with the average of 99.9% with pH 8.9~11.4. Using the same reactors, Mn removal experiments with Fe during 237 days were conducted with the influent with $40{\sim}60Mn{\cdot}mg/L$. The pH range of effluent reached to 6.1~10.0, which is slightly lower than that of effluent without Fe. S reactor showed the highest range of pH with 7.1~9.9, followed by S+L and S+G reactor. However, the efficiency of Mn removal showed S+L>S>S+G with the range of 94~100%, 68~100% and 68~100%, respectively in spite of relatively low pH range. S+L reactor showed the most resistance on Fe input, which means other mechanisms such as $MnCO_3$ formation by the carbonate prouced from the limestone or autocatalysis reaction of Mn contributed to Mn removal rather than pH related mechanisms. The evidence of reactions between carbonates and Mn, rhodochrosite ($MnCO_3$), was found from the X-ray diffraction analysis of precipitates sample from S+L reactor. From this study, the most effective reactors on Mn removal in the presence of Fe was S+L reactor. The results are expected to be applied for the Mn containing mine water treatment in the presence of Fe within the relatively low range of pH.

• Economic and Environmental Geology
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• v.36 no.4
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• pp.285-293
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• 2003

Tailings of Dukum mine in the vadose and saturated zone were investigated to reveal the mobility of metal elements and the condition of mineralogical solubility according to redox environments throughout the geochemical analysis, thermodynamic modelling, and mineralogical study for solid-samples and water samples(vadose zone; distilled water: tailings=5 : 1 reacted, saturated zone; pore-water extracted). In the vadose zone, sulfide oxidation has generated low-pH(2.72∼6.91) condition and high concentration levels of S $O_4$$^{2-}$(561∼1430mg/L) and other metals(Zn : 0.12∼l57 mg/L, Pb : 0.06∼0.83 mg/L, Cd : 0.06∼l.35 mg/L). Jarosite$(KFe_3(SO_4)_2(OH)_6)$ and gypsum$(CaSO_4{\cdot}2H_2O$) were identified on XRD patterns and thermodynamics modelling. In the saturated zone, concentration of metal ions decreased because pH values were neutral(7.25∼8.10). But Fe and Mn susceptible to redox potential increased by low-pe values(7.40∼3.40) as the depth increased. Rhodochrosite$(MnCO_3)$ identified by XRD and thermodynamics modelling suggested that $Mn^{4+}$ or $Mn^{3+}$ was reduced to $Mn^{2+}$. Along pH conditions, concentrations of dissolved metal ions has been most abundant in vadose zone throughout borehole samples. It was observed that pH had more effect on metal solubilities than redox potential. How-ever, the release of co-precipitated heavy metals following the dissolution of Fe-Mn oxyhydroxides could be the mechanism by which reduced condition affected heavy metal solubility considering the decrease of pe as depth increased in tile saturated zone.

• Economic and Environmental Geology
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• v.34 no.6
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• pp.507-522
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• 2001

At the Tongyeong mine, quartz, rhodochrosite (kutnahorite), muscovite, illite, pyrite, galena, chalcopyrite. sphalerite, acanthite, and hessite are the principal vein minerals. They were deposited under epithermal conditions in two stages. Ore mineral assemblages and associated gangue phases in stage can be clearly divided into two general associations: an early cycle (band) that appeared with introduction of most of the sulfides and electrum, and a later cycle in which base metal and carbonate-bearing assemblages (mostly rhodochrosite) became dominant. Tellurides and some electrum occur as small rounded grains within subhedral-to euhedral pyrite or anhedral galena in stageII. Sulfide mineralization is zoned from pyrite to galena and sphalerite. We have used computer modeling to simulate formation of four stages of vein genesis. The reaction of a single fluid with andesite host rock at 28$0^{\circ}C$, isobaric cooling of a single fluid from 26$0^{\circ}C$ to 12$0^{\circ}C$, and boiling and mixing of a fluid with both decreasing pressure and temperature were studied using the CHILLER program. Calculations show that the precipitation of alteration minerals is due to fluid-andesite interaction as temperature drops. Speciation calculations confirm that the hydrothermal fluids with moderately high salinities and pH 5.7 (acid), were capable of transporting significant quantities of base metals. The abundance of gold in fluid depends critically on the ratio of total base metals and iron to sulfide in the aqueous phase because gold is transported as an Au(HS)$_2$- complex, which is sensitive to sulfide activity. Modeling results for Tongyeong mineralization show strong influence of shallow hydrogenic processes such as boiling and fluid mixing. The variable handing in stageII mineralization is best explained by maltiple boilings of hydrothermal fluid followed by lateral mixing of the fluid with overlying diluted, steam-heated ground water. The degree of similarity of calculated mineral assemblages and observed electrum composition and field relationships shows the utility of the numerical simulation method in identifying chemical processes that accompany boiling and mixing in Te-bearing Au-Ag system. This has been applied in models to narrow the search area for epithermal ores.

• Journal of the Mineralogical Society of Korea
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• v.15 no.3
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• pp.231-240
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• 2002

Microbial metal reduction influences the biogeochemical cycles of carbon and metals as well as plays an important role in the bioremediation of metals, radionuclides, and organic contaminants. The use of bacteria to facilitate the production of magnetite nanoparticles and the formation of carbonate minerals may provide new biotechnological processes for material synthesis and carbon sequestration. Metal-reducing bacteria were isolated from a variety of extreme environments, such as deep terrestrial subsurface, deep marine sediments, water near Hydrothemal vents, and alkaline ponds. Metal-reducing bacteria isolated from diverse extreme environments were able to reduce Fe(III), Mn(IV), Cr(VI), Co(III), and U(VI) using short chain fatty acids and/or hydrogen as the electron donors. These bacteria exhibited diverse mineral precipitation capabilities including the formation of magnetite ($Fe_3$$O_4$), siderite ($FeCO_3$), calcite ($CaCO_3$), rhodochrosite ($MnCO_3$), vivianite [$Fe_3$($PO_4$)$_2$ .$8H_2$O], and uraninite ($UO_2$). Geochemical and environmental factors such as atmospheres, chemical milieu, and species of bacteria affected the extent of Fe(III)-reduction as well as the mineralogy and morphology of the crystalline iron mineral phases. Thermophilic bacteria use amorphous Fe(III)-oxyhydroxide plus metals (Co, Cr, Ni) as an electron acceptor and organic carbon as an electron donor to synthesize metal-substituted magnetite. Metal reducing bacteria were capable of $CO_2$conversion Into sparingly soluble carbonate minerals, such as siderite and calcite using amorphous Fe(III)-oxyhydroxide or metal-rich fly ash. These results indicate that microbial Fe(III)-reduction may not only play important roles in iron and carbon biogeochemistry in natural environments, but also be potentially useful f3r the synthesis of submicron-sized ferromagnetic materials.

• Journal of the Mineralogical Society of Korea
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• v.5 no.2
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• pp.102-108
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• 1992

The natural (Ca, Mg)-buserite has been identified from the manganese oxideores of the Janggun mine, Korea, which have been formed by supergene weathering of sedimentary-metamorphic rhodochrosite. It occurs together with rancieite forming one very fine-grained buserite-rancieite flake. This (Ca, Mg)-buserite-rancieite occurs as microcystalline flaky crystals. It precipitated around the fine-grained takanelite aggregate. Electron microprobe analyses give the formula ($Ca_{.08}Mg_{.07}Mn_{.05}^{2+})Mn_{.89}^{4+}O_2{\cdot}1.46H_2O$ for (Ca, Mg)-buserite. The dehydration experiments by relative humidity control and heating as well as rehydration experiment by relative humidity control show that (Ca, Mg)-buserite dehydrates completely at 90$^{\circ}C$ and rehydrates up to 27% of the original state. The dehydration at 26% RH (corresponding to heating to about 40$^{\circ}C$) is characterized by thedecrease in the decrease in the intensity of 9.86${\AA}$ peak with slight shifting to 9.60${\AA}$. It is due to the loss of weakly bound water molecules in the interlayer. The dehydration from 40$^{\circ}C$ to 90$^{\circ}C$ is characterized by the gradual shifting of 001 peak from 9.6${\AA}$ to 7.42${\AA}$. It is due to the loss of weakly bound water molecules in the interlayer.

• Economic and Environmental Geology
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• v.16 no.1
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• pp.1-10
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• 1983

The Yeonhwa (I, II) and Keodo mines, neighboring in the middle part of the Taebaegsan mineral belt, contain three distinct classes of skarn deposits: the zinc-lead skarn at Yeonhwa (I, II), the iron skarn at Keodo south (Jangsan orebodies), and the copper skarn at Keodo north (78 orebodies). The present study characterizes the three classes of skarn deposits mainly in terms of skarn/ore associations examined from chemical compositional point of view, and applies existing quantitative phase diagrams to some pertinent mineral assemblages in these mines. At Yeonhwa I the Wolam I orebody shows a vertical variation in skarn minerals ranging from clinopyroxene/garnet zone on the lower levels through clinopyroxene (without garnet) zone on the intermediate levels, and finally to rhodochrosite veins on the upper levels and surface. Ore minerals, sphalerite and galena, associate most closely with the intermediate clinopyroxene zone. At Keodo, the Jangsan iron skarn hosted in quartz monzodiolite as a typical endoskarn, shows a skarn zoning, from center of orebody to outer side, magnetite zone, magnetite/garnet zone, garnet clinopyroxene zone, and clinopyroxene/epidote/plagioclase zone. The 78 copper skarn in the Hwajeol limestone indicates a zoning, from quartz porphyry side toward limestone side, orthoclase/epidote zone, epidote/clinopyroxene zone, and clinopyroxene/garnet zone; chalcopyrite and other copper sulfides tend to be in clinopyroxene/garnet zone. Mioroprobe analyses of clinopyroxenes and garnets from the various skarn zones mentioned above revealed that the Yeonhwa zinc/lead skarns are characterized by johansenitic clinopyroxene (Hd 25-78, Jo 15-23) and manganoan andraditic garnet (Ad 13-97, Sp 1-24), whereas the Jangsan iron skarn at Keodo by Mn-poor diopsidic clinopyroxene (Di 78-93, Jo 0.2-1.0) and Mn-poor grossularitic grandite (Gr 65-77, Sp 0.5-1.0). The 78 copper skarn at Keodo is characterized by Mn-poor diopsidic-salite (Di 66-91, Jo 0.2-1.1) and Mn-poor andraditic grandite(Ad 40-74, Sp 0.5-1.1). The compositional charateristics of iron, copper, and zinc-lead skarns in the Yeonhwa-Keodo mines are in good correlations with those of the foreign counterparts. Compiling a $T-XCO_2$ phase diagram for the Jangsan endoskarns, a potential upper limit of temperature of the main stage of skarn formation is estimated to be about $530^{\circ}C$, and a lower limit to be $400^{\circ}C$ or below assuming $XCO_2=0.05$ at P total=1kb. Applying a published log $fS_2$-log $fo_2$ diagram to the Keodo 78 and Yeonhwa exoskarns, it is revealed that copper sulfides and zinc-lead sulfides do not co-exist stably below log $fS_2=-4$ and log $fO_2=-23$ at $T=400^{\circ}C$ and ${\times}CO=1$ atm.

• Journal of the Korean GEO-environmental Society
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• v.13 no.9
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• pp.31-44
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• 2012

Seasonal changes in groundwater geochemistry exist in Ddan-sum island. In the farming season of April, the spatial distribution of ions explains that $Fe^{2+}$, Fe(total), $Mn^{2+}$, $Ca^{2+}$, $Mg^{2+}$, $SiO_2$, ${HCO_3}^-$, and ${NO_3}^-$ are high in the center of the island, but $Na^+$ and $K^+$ are relatively low and these high anions indicates the effect of fertilizer used for strawberry cultivation. Spatial variation of ion concentration is smaller in August than April because of low agricultural activity and heavy rainfall. Geochemical type of groundwater shows that the center of island has the characteristics of recharge zone but the rim area corresponds to a mixing zone between groundwater and stream water. According to the analysis of saturation index for Fe and Mn ions, hematite, goethite, and rhodochrosite under supersaturation have a possibility of additional mineral deposition, and siderite, $Fe(OH)_3$, manganite, pyrolusite, and pyrochroite under unsaturation may exist as a type of dissolved ion.

• Economic and Environmental Geology
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• v.31 no.5
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• pp.389-398
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• 1998

The Au-Ag deposit of the Oknam mine occurs as gold-silver-bearing rhodochrosite veins in biotite schist and phyllite of the Precambriam Yulri Group. Five stages of ore deposition are recognized, each showing a definite mineral assemblage. General mineral parageneses in veins (stage III) associated with gold and silver vary inwardly from the vein margin: arsenopyrite + pyrite $\Rightarrow$ sphalerite+chalcopyrite+galena+gold $\Rightarrow$ ga1ena+Ag-bearing minerals. Fluid inclusion data indicate that temperature and salinity of ore fluids overally decreased with time: $345^{\circ}{\sim}240^{\circ}C$ and 3.4~7.8 wt. % NaCl equiv during stage I (quartz vein mineralization), $313^{\circ}{\sim}207^{\circ}C$ and 2.3~8.7 wt.% NaCl equiv during manganese-bearing carbonate stages (II and III), and $328^{\circ}{\sim}213^{\circ}C$ and 3.6-5.4 wt.% NaCl equiv during stage IV (quartz vein mineralization). The ore fluids probably evolved through repeated pulses of boiling and later mixing with cooler and more dilute meteoric waters. Fluid inclusion data and geologic arguments indicate that pressures during the mineralization were in the range of 90 to 340 bars. Gold occurs as silver-rich electrums (21 to 29 atom. % Au) and was deposited at temperatures between $300^{\circ}$ and $240^{\circ}C$. Thermochemical calculations suggest that gold was deposited as a combined result of increase in pH and decreases in temperature, $fs_2$ and $fo_2$.